EP1122229A1 - Process for the preparation of condensed cyclopentadiene derivatives, 1, 3 disubstituted derivatives and metallocene type compounds containing them as ligand - Google Patents

Process for the preparation of condensed cyclopentadiene derivatives, 1, 3 disubstituted derivatives and metallocene type compounds containing them as ligand Download PDF

Info

Publication number
EP1122229A1
EP1122229A1 EP01300942A EP01300942A EP1122229A1 EP 1122229 A1 EP1122229 A1 EP 1122229A1 EP 01300942 A EP01300942 A EP 01300942A EP 01300942 A EP01300942 A EP 01300942A EP 1122229 A1 EP1122229 A1 EP 1122229A1
Authority
EP
European Patent Office
Prior art keywords
cyclized
crosslink
cyclopentadiene
general formula
membered ring
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP01300942A
Other languages
German (de)
French (fr)
Other versions
EP1122229B1 (en
Inventor
Keiichi c/o Honshu Chemical Industry Co Yokoyama
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honshu Chemical Industry Co Ltd
Original Assignee
Honshu Chemical Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Honshu Chemical Industry Co Ltd filed Critical Honshu Chemical Industry Co Ltd
Publication of EP1122229A1 publication Critical patent/EP1122229A1/en
Application granted granted Critical
Publication of EP1122229B1 publication Critical patent/EP1122229B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/45—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing nine carbon atoms
    • C07C13/465—Indenes; Completely or partially hydrogenated indenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
    • C12C11/00—Fermentation processes for beer
    • C12C11/02—Pitching yeast
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/14—All rings being cycloaliphatic
    • C07C2602/24—All rings being cycloaliphatic the ring system containing nine carbon atoms, e.g. perhydroindane

Definitions

  • the present invention relates to a process for producing a crosslink-cyclized cyclopentadiene, a crosslink-cyclized cyclopentadiene, a dihalobis ( ⁇ -crosslink-cyclized cyclopentadienyl)metal compound containing the crosslink-cyclized cyclopentadiene, and a process for producing the same.
  • Cyclopentadienes are widely used not only as monomers for producing various polymers but also in the production of metallocene compounds of transition metals such as titanium, zirconium and hafnium.
  • the metallocene compounds are widely utilized as effective ligand components of olefin polymerization catalysts.
  • Japanese Patent Laid-open Publication No. 62(1987)-72630 describes a process comprising reacting dicyclopentadiene with methanol in the presence of an alkali metal oxide.
  • this process has a drawback in that the desired product cannot be efficiently obtained due to, for example, by-products of position isomers.
  • Japanese Patent Laid-open Publication No. 3(1991)-215437 describes a process comprising performing a vapor-phase cyclization dehydration of 5-methyl-5-hexen-2-one in the presence of a catalyst such as alumina.
  • a catalyst such as alumina.
  • this process has drawbacks in that the raw materials are expensive and that the reaction must be performed in a vapor phase at such high temperatures as over 200°C to thereby necessitate special apparatus.
  • Japanese Patent Laid-open Publication No. 8(1996)-208533 describes a process for producing a cyclopentadiene, comprising performing a cyclization dehydration of an unsaturated carbonyl compound in the presence of a solid acid catalyst in a vapor phase.
  • this process also has a drawback in that the reaction comprises a cyclization dehydration in a vapor phase and the reaction temperature is as high as 330 to 430°C (as indicated in working example portions) to thereby necessitate special apparatus.
  • crosslink-cyclized cyclopentadiene of the general formula the formula has been shown in, for example, Japanese Patent Laid-open Publication No. 9(1997)-132537 in connection with the use as ligands of metallocene catalysts for olefin polymerization.
  • R 1 and R 2 are alkyl groups and as to the process for producing the same.
  • synthetic example published for such a compound as far as the inventors' investigations have been made.
  • the present invention has been made with a view toward solving the above problems of the prior art. It is an object of the present invention to provide a process for producing a crosslink-cyclized cyclopentadiene with high yield under mild conditions without the need to install special apparatus. It is another object of the present invention to provide a crosslink-cyclized cyclopentadiene comprising a cyclopentadiene substituted with two alkyl groups.
  • the inventors have made extensive and intensive studies with a view toward solving the above problems. As a result, they have found a novel process for producing a crosslink-cyclized cyclopentadiene with high yield under mild conditions without the need to install special apparatus, wherein a crosslink-cyclized cyclopentenone is reacted with an alkali metal hydride to thereby reduce the same and wherein the thus obtained crosslink-cyclized cyclopentenol is reacted with a dehydrating agent to thereby reduce the same.
  • the inventors have specifically found a novel crosslink-cyclized cyclopentadiene comprising a cyclopentadienyl substituted with two alkyl groups.
  • the alkali metal hydride is preferably an alkali metal borohydride compound, still preferably sodium borohydride or potassium borohydride.
  • the reduction step A is preferably performed at -10 to 100°C.
  • the dehydrating agent is preferably a strong acid.
  • the dehydration step B is preferably performed at -10 to 100°C.
  • the dihalobis ( ⁇ -crosslink-cyclized cyclopentadienyl)metal compound of the general formula (V) according to the present invention is obtained by reacting a cyclopentadiene of the general formula (IV) with a metal halide;
  • Fig. 1 is an NMR spectrum chart of 7,9-dimethylbicyclo[4,3,0]nona-1(9)-en-8-ol.
  • Fig. 2 is an NMR spectrum chart of 7,9-dimethylbicyclo[4,3,0]nonadiene.
  • Fig. 3 is an NMR spectrum chart of dichlorobis ⁇ 7,9-dimethylbicyclo[4,3,0]nonadienyl ⁇ zirconium.
  • a cyclopentenone is reacted with an alkali metal hydride to thereby reduce the cyclopentenone (reduction step A) into a cyclopentenol.
  • the cyclopentenol is reacted with a dehydrating agent to thereby dehydrate the cyclopentenol (dehydration step B) into a crosslink-cyclized cyclopentadiene.
  • crosslink-cyclized cyclopentenone as a starting material of the crosslink-cyclized cyclopentadiene of the present invention is represented by the general formula (I): wherein each of R 1 and R 2 independently represents a hydrogen atom or a linear or branched saturated alkyl group having 1 to 6 carbon atoms, and n is an integer of 3 to 10.
  • the linear or branched saturated alkyl group having 1 to 6 carbon atoms, represented by R 1 and R 2 , can be, for example, any of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, n-hexyl and isohexyl.
  • crosslink-cyclized cyclopentenone represented by the general formula (I) can be, for example, any of; crosslink-cyclized cyclopentenones of the general formula (I) wherein both R 1 and R 2 are hydrogen atoms, such as bicyclo[3,3,0]octa-1(8)-en-7-one, bicyclo[4,3,0]nona-1(9)-en-8-one, bicyclo[5,3,0]deca-1(10)-en-9-one, bicyclo[6,3,0]undeca-1(11)-en-10-one, bicyclo[7,3,0]dodeca-1(12)-en-11-one, bicyclo[8,3,0]trideca-1(13)-en-12-one, bicyclo[9,3,0]tetradeca-1(14)-en-13-one, and bicyclo[10,3,0]pentadeca-1(15)-en-14-one; crosslink-cyclized cyclopentenones of the general formula (I) wherein
  • crosslink-cyclized cyclopentenones can be synthesized by known methods, for example, the method described in J. Am. Chem. Soc., 100, 1799 (1978).
  • the alkali metal hydride for use in the reduction step A of the present invention can be, for example, an alkali metal borohydride compound such as sodium borohydride or potassium borohydride, or an alkali metal aluminum alkoxyhydride compound. Of these, sodium borohydride and potassium borohydride are preferred, and sodium borohydride is especially preferred.
  • the alkali metal hydride be used in a molar amount of 0.5 to 8 times, especially 1 to 4 times, and still especially 2 to 3 times, that of the above crosslink-cyclized cyclopentenone.
  • the reduction reaction of the reduction step A of the present invention is preferably performed in the presence of a solvent.
  • a solvent there can be mentioned, for example, an alcohol such as methanol or ethanol, an ether such as tetrahydrofuran, 1,3-dioxolane, dimethoxyethane, dioxane, diethyl ether or dibutyl ether, water and DMF.
  • the above solvents can be used individually or in combination.
  • the solvent be used in an amount of 1 to 20 parts by weight, especially 3 to 8 parts by weight, and still especially 4 to 6 parts by weight, per 100 parts by weight of alkali metal hydride.
  • reaction temperature be in the range of about -10 to 100°C, especially -10 to 80°C, and still especially 0 to 30°C. It is generally preferred that the reaction time be in the range of 30 min to 24 hr, especially 2 to 8 hr.
  • This reaction is preferably performed in an atmosphere of inert gas such as nitrogen gas.
  • the reduction reaction can be selectively advanced by carrying out the reaction of crosslink-cyclized cyclopentenone and alkali metal hydride under the above conditions to thereby enable obtaining the desired crosslink-cyclized cyclopentenol with high yield.
  • the product can be obtained by, for example, sequentially performing acid neutralization of a solution containing the reaction product, isolation and purification. Instead, without isolating the reaction product, the solution containing the reaction product can directly be subjected to the subsequent dehydration reaction (B) of formed crosslink-cyclized cyclopentenol.
  • the product yield is generally in the range of about 70 to 90% based on the cyclopentenol.
  • the dehydrating agent for use in the dehydration reaction of cyclopentenol of the general formula (II) in the dehydration step B of the present invention is preferably an acid dehydrating agent, still preferably a strong acid.
  • the acid dehydrating agent there can be mentioned, for example, hydrochloric acid, paratoluenesulfonic acid and sulfuric acid.
  • the dehydrating agent be used in a molar amount of 0.01 to 1.0 time, especially 0.05 to 0.5 time, and still especially 0.10 to 0.25 time, that of the above crosslink-cyclized cyclopentenol.
  • the dehydration reaction of the dehydration step B of the present invention is preferably performed in the presence of a solvent.
  • a solvent Any solvents can be employed as long as they are inert to the reaction.
  • solvents used in the above reduction step A and hydrocarbon solvents can be employed as the solvent.
  • polar solvents capable of oil/water separation for example, ether solvents such as tetrahydrofuran, 1,3-dioxolane, dimethoxyethane, dioxane, diethyl ether and dibutyl ether. These solvents can be used individually or in combination.
  • the solvent be used in an amount of 1 to 20 parts by weight, especially 3 to 10 parts by weight, and still especially 5 to 7 parts by weight, per 100 parts by weight of crosslink-cyclized cyclopentenol.
  • reaction temperature be in the range of about -10 to 60°C, especially 0 to 40°C, and still especially 10 to 30°C. It is generally preferred that the reaction time be in the range of 1 to 48 hr, especially 4 to 12 hr. This reaction is preferably performed in an atmosphere of inert gas such as nitrogen gas.
  • the desired crosslink-cyclized cyclopentadiene can be obtained by carrying out the reaction of crosslink-cyclized cyclopentenol and dehydrating agent under the above conditions.
  • the product can be obtained by, for example, sequentially performing neutralization of a solution containing the reaction product, isolation and purification.
  • the product yield is generally in the range of about 70 to 90% based on the cyclopentenone.
  • the thus obtained product is crosslink-cyclized cyclopentadiene of the general formula (III): wherein R 1 , R 2 and n are as defined above with respect to the general formula (I), and the broken line in the 5-membered ring denotes that the 5-membered ring has two double bonds.
  • the crosslink-cyclized cyclopentadiene obtained by the present invention can be, for example, any of: crosslink-cyclized cyclopentadienes of the general formula (III) wherein both R 1 and R 2 are hydrogen atoms, such as bicyclo[3,3,0]octadiene, bicyclo[4,3,0]nonadiene, bicyclo[5,3,0]decadiene, bicyclo[6,3,0]undecadiene, bicyclo[7,3,0]dodecadiene, bicyclo[8,3,0]tridecadiene, bicyclo[9,3,0]tetradecadiene, and bicyclo[10,3,0]pentadecadiene; crosslink-cyclized cyclopentadienes of the general formula (III) wherein either of R 1 and R 2 is an alkyl substituent, such as 6-methylbicyclo[3,3,0]octadiene, 8-methylbicyclo[3,3,0]octadiene
  • the double bonds of these diene compounds may contain position isomers as a result of isomerization.
  • the second invention provides crosslink-cyclized cyclopentadienes of the general formula (IV): wherein each of R 1 and R 2 independently represents a linear or branched saturated alkyl group having 1 to 6 carbon atoms, n is an integer of 3 to 10, and the broken line in the 5-membered ring denotes that the 5-membered ring has two double bonds.
  • crosslink-cyclized cyclopentadienes are novel compounds, examples of which include 6,8-dimethylbicyclo[3,3,0]octadiene, 6,8-diethylbicyclo[3,3,0]octadiene, 6,8-diisopropylbicyclo[3,3,0]octadiene, 6-methyl-8-n-butylbicyclo[3,3,0]octadiene, 7,9-dimethylbicyclo[4,3,0]nonadiene, 7,9-diethylbicyclo[4,3,0]nonadiene, 7,9-diisopropylbicyclo[4,3,0]nonadiene, 7-methyl-9-n-butylbicyclo[4,3,0]nonadiene, 8,10-dimethylbicyclo[5,3,0]decadiene, 8,10-diethylbicyclo[5,3,0]decadiene, 8,10-diisopropylbicyclo[
  • the double bonds of these diene compounds may contain position isomers as a result of isomerization.
  • the dihalobis( ⁇ -crosslink-cyclized cyclopentadienyl)metal compound according to the present invention can be synthesized by reacting the above obtained crosslink-cyclized cyclopentadiene of the general formula (IV) with a metal halide in the presence of a base.
  • dihalobis ( ⁇ -crosslink-cyclized cyclopentadienyl)metal compound can be synthesized by:
  • the process comprising reacting the crosslink-cyclized cyclopentadiene with a base in a solvent in advance and mixing the resultant reaction mixture with a metal halide suspension is preferably employed.
  • the base for use in the present invention can be, for example, n-butyllithium or sodium hydride.
  • solvents inert to the reaction for example, an ether such as tetrahydrofuran, 1,3-dioxolane, dimethoxyethane, dioxane, diethyl ether or dibutyl ether, a saturated aliphatic or alicyclic solvent such as n-hexane or cyclohexane and an aromatic solvent such as toluene or benzene.
  • an ether such as tetrahydrofuran, 1,3-dioxolane, dimethoxyethane, dioxane, diethyl ether or dibutyl ether
  • a saturated aliphatic or alicyclic solvent such as n-hexane or cyclohexane
  • aromatic solvent such as toluene or benzene.
  • the base be used in a molar amount of 0.8 to 1.5 times, especially 0.9 to 1.2 times, and still especially 0.98 to 1.08 times, that of the above crosslink-cyclized cyclopentadiene.
  • the temperature at which the crosslink-cyclized cyclopentadiene is reacted with the base is generally in the range of -20 to 50°C, preferably 0 to 30°C.
  • the reaction time is generally in the range of 30 to 48 hr, preferably 5 to 30 hr.
  • the metal halide compound for use in the present invention can be any of a titanium halide, a zirconium halide and a hafnium halide. Of these, a zirconium halide is preferably employed.
  • the metal halide compound can be any of fluorides, chlorides, bromides and iodides of titaniums (II), (III) and (IV); fluorides, chlorides, bromides and iodides of zirconiums (II), (III) and (IV); and fluorides, chlorides, bromides and iodides of hafniums (II), (III) and (IV).
  • titanium (IV), zirconium (IV) and hafnium (IV) halides are preferred, and titanium tetrachloride, zirconium tetrachloride and hafnium tetrachloride are especially preferred.
  • solvents inert to the reaction for example, hexane, heptane, toluene and ethers such as tetrahydrofuran, 1,3-dioxolane, dimethoxyethane, dioxane, diethyl ether and dibutyl ether.
  • the metal halide be used in a molar amount of 0.3 to 0.8 time, especially 0.4 to 0.6 time, and still especially 0.45 to 0.55 time, that of the crosslink-cyclized cyclopentadiene.
  • the dihalobis( ⁇ -crosslink-cyclized cyclopentadienyl)metal compound of the present invention can be obtained by adding the suspension of metal halide to the reaction mixture of crosslink-cyclized cyclopentadiene and base to thereby effect a reaction therebetween.
  • the reaction temperature is generally in the range of -20 to 50°C, preferably 0 to 30°C.
  • the reaction time is generally in the range of 3 to 72 hr, preferably 10 to 48 hr.
  • dihalobis( ⁇ -crosslink-cyclized cyclopentadienyl)metal compound is represented by the following general formula (V), and finds applications as an olefin polymerization catalyst, as a carbometallization agent for acetylene compounds, in the synthesis of a starting material of monohydride homologues and as a vulcanizing agent for silicones and rubbers; wherein each of R 1 and R 2 independently represents a linear or branched saturated alkyl group having 1 to 6 carbon atoms; n is an integer of 3 to 10; M represents Ti, Zr or Hf; and X represents a halogen atom selected from among a chlorine atom, a bromine atom, an iodine atom and a fluorine atom.
  • the dihalobis ( ⁇ -crosslink-cyclized cyclopentadienyl)metal compounds of the general formula (V) are novel compounds.
  • Preferred products are, for example, dichlorobis ( ⁇ -crosslink-cyclized cyclopentadienyl) titanium, dichlorobis ( ⁇ -crosslink-cyclized cyclopentadienyl)zirconium and dichlorobis ( ⁇ -crosslink-cyclized cyclopentadienyl)hafnium.
  • the process for producing a crosslink-cyclized cyclopentadiene according to the first invention enables producing a crosslink-cyclized cyclopentadiene with high yield under mild conditions without the need to install special apparatus.
  • the second invention enables providing a novel crosslink-cyclized cyclopentadiene.
  • the third invention enables providing a dihalobis ( ⁇ -crosslink-cyclized cyclopentadienyl)metal compound containing the above crosslink-cyclized cyclopentadiene as ligands.
  • a THF (6g) solution containing 2.35 g (10 mmol) of 7,9-dimethylbicyclo[4,3,0]nonadiene synthesized in the same manner as in Example 1 was cooled to 5°C in a nitrogen atmosphere.
  • 6.5 ml (1.6 mmol) of a hexane solution of n-BuLi (10.4 mmol) was dropped into the solution.
  • the reaction mixture was slowly heated up to room temperature (25°C). At this temperature, the mixture was agitated for 24 hr. Thus, a yellowish-brown suspension was obtained.
  • the obtained yellowish-brown suspension was dropped into a suspension of 1.16 g (5 mmol) of zirconium tetrachloride in 10 g of heptane while maintaining the temperature at 10°C or below by cooling with ice. Thereafter, the reaction mixture was heated up to room temperature (25°C) and agitated for 48 hr. Thus, a blackish-brown suspension was obtained. This blackish-brown suspension was filtered to thereby obtain a yellowish-brown solution, from which the solvent was distilled off. Thus, 1.02 g of yellowish-brown viscous oil was obtained. 10 g of heptane was added to the yellowish-brown viscous oil. Precipitated crystal was collected by filtration. Thus, 20 mg of desired crystal was obtained. The purity was about 90%, and the yield was 1% based on the 7,9-dimethylbicyclo[4,3,0]nonadiene.

Landscapes

  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Mycology (AREA)
  • Food Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Microbiology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

A process for producing a crosslink-cyclized cyclopentadiene, comprising the steps of reacting a cyclopentenone with an alkali metal hydride to thereby reduce the cyclopentenone (reduction step A) into a cyclopentenol; and reacting the cyclopentenol with a dehydrating agent to thereby dehydrate the cyclopentenol (dehydration step B) into a crosslink-cyclized cyclopentadiene of the general formula (III):
Figure 80000001
   wherein each of R1 and R2 independently represents a hydrogen atom or a linear or branched saturated alkyl group having 1 to 6 carbon atoms, n is an integer of 3 to 10, and the broken line in the 5-membered ring denotes that the 5-membered ring has two double bonds.

Description

    FIELD OF THE INVENTION
  • The present invention relates to a process for producing a crosslink-cyclized cyclopentadiene, a crosslink-cyclized cyclopentadiene, a dihalobis (η-crosslink-cyclized cyclopentadienyl)metal compound containing the crosslink-cyclized cyclopentadiene, and a process for producing the same.
    • BACKGROUND OF THE INVENTION
  • Cyclopentadienes are widely used not only as monomers for producing various polymers but also in the production of metallocene compounds of transition metals such as titanium, zirconium and hafnium. The metallocene compounds are widely utilized as effective ligand components of olefin polymerization catalysts.
  • Regarding the conventional production of a crosslink-cyclized cyclopentadiene, for example, with respect to the process for producing 1,3-dimethylcyclopentadiene, Japanese Patent Laid-open Publication No. 62(1987)-72630 describes a process comprising reacting dicyclopentadiene with methanol in the presence of an alkali metal oxide. However, this process has a drawback in that the desired product cannot be efficiently obtained due to, for example, by-products of position isomers.
  • Further, Japanese Patent Laid-open Publication No. 3(1991)-215437 describes a process comprising performing a vapor-phase cyclization dehydration of 5-methyl-5-hexen-2-one in the presence of a catalyst such as alumina. However, this process has drawbacks in that the raw materials are expensive and that the reaction must be performed in a vapor phase at such high temperatures as over 200°C to thereby necessitate special apparatus.
  • Still further, Japanese Patent Laid-open Publication No. 8(1996)-208533 describes a process for producing a cyclopentadiene, comprising performing a cyclization dehydration of an unsaturated carbonyl compound in the presence of a solid acid catalyst in a vapor phase. However, this process also has a drawback in that the reaction comprises a cyclization dehydration in a vapor phase and the reaction temperature is as high as 330 to 430°C (as indicated in working example portions) to thereby necessitate special apparatus.
  • With respect to a crosslink-cyclized cyclopentadiene of the general formula:
    Figure 00030001
    the formula has been shown in, for example, Japanese Patent Laid-open Publication No. 9(1997)-132537 in connection with the use as ligands of metallocene catalysts for olefin polymerization. However, there is no particular teaching having been published as to a crosslink-cyclized cyclopentadiene wherein both R1 and R2 are alkyl groups and as to the process for producing the same. Further, there is no particular synthetic example published for such a compound as far as the inventors' investigations have been made.
    • OBJECT OF THE INVENTION
  • The present invention has been made with a view toward solving the above problems of the prior art. It is an object of the present invention to provide a process for producing a crosslink-cyclized cyclopentadiene with high yield under mild conditions without the need to install special apparatus. It is another object of the present invention to provide a crosslink-cyclized cyclopentadiene comprising a cyclopentadiene substituted with two alkyl groups.
  • It is further objects of the present invention to provide a dihalobis(η-crosslink-cyclized alkyl-substituted cyclopentadienyl)metal compound wherein the above crosslink-cyclized cyclopentadiene is incorporated and to provide a process for producing the same.
    • SUMMARY OF THE INVENTION
  • The inventors have made extensive and intensive studies with a view toward solving the above problems. As a result, they have found a novel process for producing a crosslink-cyclized cyclopentadiene with high yield under mild conditions without the need to install special apparatus, wherein a crosslink-cyclized cyclopentenone is reacted with an alkali metal hydride to thereby reduce the same and wherein the thus obtained crosslink-cyclized cyclopentenol is reacted with a dehydrating agent to thereby reduce the same.
  • In addition, the inventors have specifically found a novel crosslink-cyclized cyclopentadiene comprising a cyclopentadienyl substituted with two alkyl groups.
  • Moreover, the inventors have found a novel dihalobis (η-crosslink-cyclized alkyl-substituted cyclopentadienyl)metal compound wherein the above crosslink-cyclized cyclopentadiene is incorporated and a process for producing the same. The present invention has been completed on the basis of these findings.
  • According to the first invention, there is provided a process for producing a crosslink-cyclized cyclopentadiene, comprising the steps of;
  • reacting a cyclopentenone of the general formula (I) with an alkali metal hydride;
    Figure 00050001
  • wherein each of R1 and R2 independently represents a hydrogen atom or a linear or branched saturated alkyl group having 1 to 6 carbon atoms, and n is an integer of 3 to 10,
  • to thereby reduce the cyclopentenone (reduction step A) into a cyclopentenol of the general formula (II):
    Figure 00060001
  • wherein R1, R2 and n are as defined above with respect to the general formula (I); and
  • reacting the cyclopentenol with a dehydrating agent to thereby dehydrate the cyclopentenol (dehydration step B) into a crosslink-cyclized cyclopentadiene of the general formula (III):
    Figure 00060002
  • wherein R1, R2 and n are as defined above with respect to the general formula (I), and the broken line in the 5-membered ring denotes that the 5-membered ring has two double bonds.
  • The alkali metal hydride is preferably an alkali metal borohydride compound, still preferably sodium borohydride or potassium borohydride. The reduction step A is preferably performed at -10 to 100°C. The dehydrating agent is preferably a strong acid. The dehydration step B is preferably performed at -10 to 100°C.
  • According to the second invention, there is provided a crosslink-cyclized cyclopentadiene of the general formula (IV):
    Figure 00070001
       wherein each of R1 and R2 independently represents a linear or branched saturated alkyl group having 1 to 6 carbon atoms, n is an integer of 3 to 10, and the broken line in the 5-membered ring denotes that the 5-membered ring has two double bonds.
  • According to the third aspect of the present invention, there is provided a dihalobis (η-crosslink-cyclized cyclopentadienyl)metal compound of the general formula (V):
    Figure 00080001
       wherein each of R1 and R2 independently represents a linear or branched saturated alkyl group having 1 to 6 carbon atoms; n is an integer of 3 to 10; M represents Ti, Zr or Hf; and X represents a halogen atom selected from among a chlorine atom, a bromine atom, an iodine atom and a fluorine atom.
  • The dihalobis (η-crosslink-cyclized cyclopentadienyl)metal compound of the general formula (V) according to the present invention is obtained by reacting a cyclopentadiene of the general formula (IV) with a metal halide;
    Figure 00090001
  • wherein R1, R2 and n are as defined above with respect to the general formula (V), and the broken line in the 5-membered ring denotes that the 5-membered ring has two double bonds,
  • this reaction being performed in the presence of a base.
    • BRIEF DESCRIPTION OF THE DRAWING
  • Fig. 1 is an NMR spectrum chart of 7,9-dimethylbicyclo[4,3,0]nona-1(9)-en-8-ol.
  • Fig. 2 is an NMR spectrum chart of 7,9-dimethylbicyclo[4,3,0]nonadiene.
  • Fig. 3 is an NMR spectrum chart of dichlorobis{7,9-dimethylbicyclo[4,3,0]nonadienyl}zirconium.
    • DETAILED DESCRIPTION OF THE INVENTION
  • The process for producing a crosslink-cyclized cyclopentadiene according to the first invention, the crosslink-cyclized cyclopentadiene according to the second invention and the dihalobis(η-crosslink-cyclized cyclopentadienyl)metal comprising crosslink-cyclized cyclopentadiene according to the third invention together with the process for producing the same will be described in detail below.
    • [Process for producing crosslink-cyclized cyclopentadiene]
  • In the process for producing a crosslink-cyclized cyclopentadiene according to the first invention, first, a cyclopentenone is reacted with an alkali metal hydride to thereby reduce the cyclopentenone (reduction step A) into a cyclopentenol. Thereafter, the cyclopentenol is reacted with a dehydrating agent to thereby dehydrate the cyclopentenol (dehydration step B) into a crosslink-cyclized cyclopentadiene.
    • Crosslink-cyclized cyclopentenone
  • The crosslink-cyclized cyclopentenone as a starting material of the crosslink-cyclized cyclopentadiene of the present invention is represented by the general formula (I):
    Figure 00110001
       wherein each of R1 and R2 independently represents a hydrogen atom or a linear or branched saturated alkyl group having 1 to 6 carbon atoms, and n is an integer of 3 to 10.
  • The linear or branched saturated alkyl group having 1 to 6 carbon atoms, represented by R1 and R2, can be, for example, any of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, n-hexyl and isohexyl. The above crosslink-cyclized cyclopentenone represented by the general formula (I) can be, for example, any of; crosslink-cyclized cyclopentenones of the general formula (I) wherein both R1 and R2 are hydrogen atoms, such as bicyclo[3,3,0]octa-1(8)-en-7-one, bicyclo[4,3,0]nona-1(9)-en-8-one, bicyclo[5,3,0]deca-1(10)-en-9-one, bicyclo[6,3,0]undeca-1(11)-en-10-one, bicyclo[7,3,0]dodeca-1(12)-en-11-one, bicyclo[8,3,0]trideca-1(13)-en-12-one, bicyclo[9,3,0]tetradeca-1(14)-en-13-one, and bicyclo[10,3,0]pentadeca-1(15)-en-14-one; crosslink-cyclized cyclopentenones of the general formula (I) wherein either of R1 and R2 is an alkyl substituent, such as
       6-methylbicyclo[3,3,0]octa-1(8)-en-7-one, 8-methylbicyclo[3,3,0]octa-1(8)-en-7-one, 6-ethylbicyclo[3,3,0]octa-1(8)-en-7-one, 8-ethylbicyclo[3,3,0]octa-1(8)-en-7-one, 6-isopropylbicyclo[3,3,0]octa-1(8)-en-7-one, 8-isopropylbicyclo[3,3,0]octa-1(8)-en-7-one, 8-n-butylbicyclo[3,3,0]octa-1(8)-en-7-one, 7-methylbicyclo[4,3,0]nona-1(9)-en-8-one, 9-methylbicyclo[4,3,0]nona-1(9)-en-8-one, 7-ethylbicyclo[4,3,0]nona-1(9)-en-8-one, 9-ethylbicyclo[4,3,0]nona-1(9)-en-8-one, 7-isopropylbicyclo[4,3,0]nona-1(9)-en-8-one, 9-isopropylbicyclo[4,3,0]nona-1(9)-en-8-one, 9-n-butylbicyclo[4,3,0]nona-1(9)-en-8-one, 8-methylbicyclo[5,3,0]deca-1(10)-en-9-one, 10-methylbicyclo[5,3,0]deca-1(10)-en-9-one, 8-ethylbicyclo[5,3,0]deca-1(10)-en-9-one, 10-ethylbicyclo[5,3,0]deca-1(10)-en-9-one, 8-isopropylbicyclo[5,3,0]deca-1(10)-en-9-one, 10-isopropylbicyclo[5,3,0]deca-1(10)-en-9-one, 10-n-butylbicyclo[5,3,0]deca-1(10)-en-9-one, 9-methylbicyclo[6,3,0]undeca-1(11)-en-10-one, 11-methylbicyclo[6,3,0]undeca-1(11)-en-10-one, 9-ethylbicyclo[6,3,0]undeca-1(11)-en-10-one, 11-ethylbicyclo[6,3,0]undeca-1(11)-en-10-one, 9-isopropylbicyclo[6,3,0]undeca-1(11)-en-10-one, 11-isopropylbicyclo[6,3,0]undeca-1(11)-en-10-one, 11-n-butylbicyclo[6,3,0]undeca-1(11)-en-10-one, 10-methylbicyclo[7,3,0]dodeca-1(12)-en-11-one, 12-methylbicyclo[7,3,0]dodeca-1(12)-en-11-one, 10-ethylbicyclo[7,3,0]dodeca-1(12)-en-11-one, 12-ethylbicyclo[7,3,0]dodeca-1(12)-en-11-one, 10-isopropylbicyclo[7,3,0]dodeca-1(12)-en-11-one, 12-isopropylbicyclo[7,3,0]dodeca-1(12)-en-11-one, 12-n-butylbicyclo[7,3,0]dodeca-1(12)-en-11-one, 11-methylbicyclo[8,3,0]trideca-1(13)-en-12-one, 13-methylbicyclo[8,3,0]trideca-1(13)-en-12-one, 11-ethylbicyclo[8,3,0]trideca-1(13)-en-12-one, 13-ethylbicyclo[8,3,0]trideca-1(13)-en-12-one, 11-isopropylbicyclo[8,3,0]trideca-1(13)-en-12-one, 13-isopropylbicyclo[8,3,0]trideca-1(13)-en-12-one, 13-n-butylbicyclo[8,3,0]trideca-1(13)-en-12-one, 12-methylbicyclo[9,3,0]tetradeca-1(14)-en-13-one, 14-methylbicyclo[9,3,0]tetradeca-1(14)-en-13-one, 12-ethylbicyclo[9,3,0]tetradeca-1(14)-en-13-one, 14-ethylbicyclo[9,3,0]tetradeca-1(14)-en-13-one, 12-isopropylbicyclo[9,3,0]tetradeca-1(14)-en-13-one, 14-isopropylbicyclo[9,3,0]tetradeca-1(14)-en-13-one, 14-n-butylbicyclo[9,3,0]tetradeca-1(14)-en-13-one, 13-methylbicyclo[10,3,0]pentadeca-1(15)-en-14-one, 15-methylbicyclo[10,3,0]pentadeca-1(15)-en-14-one, 13-ethylbicyclo[10,3,0]pentadeca-1(15)-en-14-one, 15-ethylbicyclo[10,3,0]pentadeca-1(15)-en-14-one, 13-isopropylbicyclo[10,3,0]pentadeca-1(15)-en-14-one, 15-isopropylbicyclo[10,3,0]pentadeca-1(15)-en-14-one, and
    15-n-butylbicyclo[10,3,0]pentadeca-1(15)-en-14-one; and
    crosslink-cyclized cyclopentenones of the general formula (I) wherein both R1 and R2 are alkyl substituents, such as
       6,8-dimethylbicyclo[3,3,0]octa-1(8)-en-7-one, 6,8-diethylbicyclo[3,3,0]octa-1(8)-en-7-one, 6,8-diisopropylbicyclo[3,3,0]octa-1(8)-en-7-one, 6-methyl-8-n-butylbicyclo[3,3,0]octa-1(8)-en-7-one, 7,9-dimethylbicyclo[4,3,0]nona-1(9)-en-8-one, 7,9-diethylbicyclo[4,3,0]nona-1(9)-en-8-one, 7,9-diisopropylbicyclo[4,3,0]nona-1(9)-en-8-one, 7-methyl-9-n-butylbicyclo[4,3,0]nona-1(9)-en-8-one, 8,10-dimethylbicyclo[5,3,0]deca-1(10)-en-9-one, 8,10-diethylbicyclo[5,3,0]deca-1(10)-en-9-one, 8,10-diisopropylbicyclo[5,3,0]deca-1(10)-en-9-one, 8-methyl-10-n-butylbicyclo[5,3,0]deca-1(10)-en-9-one, 9,11-dimethylbicyclo[6,3,0]undeca-1(11)-en-10-one, 9,11-diethylbicyclo[6,3,0]undeca-1(11)-en-10-one, 9,11-diisopropylbicyclo[6,3,0]undeca-1(11)-en-10-one, 9-methyl-11-n-butylbicyclo[6,3,0]undeca-1(11)-en-10-one,
    10,12-dimethylbicyclo[7,3,0]dodeca-1(12)-en-11-one, 10,12-diethylbicyclo[7,3,0]dodeca-1(12)-en-11-one, 10,12-diisopropylbicyclo[7,3,0]dodeca-1(12)-en-11-one,
    10-methyl-12-n-butylbicyclo[7,3,0]dodeca-1(12)-en-11-one,
    11,13-dimethylbicyclo[8,3,0]trideca-1(13)-en-12-one, 11,13-diethylbicyclo[8,3,0]trideca-1(13)-en-12-one, 11,13-diisopropylbicyclo[8,3,0]trideca-1(13)-en-12-one,
    11-methyl-13-n-butylbicyclo[8,3,0]trideca-1(13)-en-12-one,
    12,14-dimethylbicyclo[9,3,0]tetradeca-1(14)-en-13-one,
    12,14-diethylbicyclo[9,3,0]tetradeca-1(14)-en-13-one,
    12,14-diisopropylbicyclo[9,3,0]tetradeca-1(14)-en-13-one,
    12-methyl-14-n-butylbicyclo[9,3,0]tetradeca-1(14)-en-13-one,
    13,15-dimethylbicyclo[10,3,0]pentadeca-1(15)-en-14-one,
    13,15-diethylbicyclo[10,3,0]pentadeca-1(15)-en-14-one,
    13,15-diisopropylbicyclo[10,3,0]pentadeca-1(15)-en-14-one, and
    13-methyl-15-n-butylbicyclo[10,3,0]pentadeca-1(15)-en-14-one.
  • These crosslink-cyclized cyclopentenones can be synthesized by known methods, for example, the method described in J. Am. Chem. Soc., 100, 1799 (1978).
    • [Reduction step A] Alkali metal hydride
  • The alkali metal hydride for use in the reduction step A of the present invention can be, for example, an alkali metal borohydride compound such as sodium borohydride or potassium borohydride, or an alkali metal aluminum alkoxyhydride compound. Of these, sodium borohydride and potassium borohydride are preferred, and sodium borohydride is especially preferred.
  • It is preferred that the alkali metal hydride be used in a molar amount of 0.5 to 8 times, especially 1 to 4 times, and still especially 2 to 3 times, that of the above crosslink-cyclized cyclopentenone.
    • Solvent (reduction step A)
  • The reduction reaction of the reduction step A of the present invention is preferably performed in the presence of a solvent. As a suitable solvent, there can be mentioned, for example, an alcohol such as methanol or ethanol, an ether such as tetrahydrofuran, 1,3-dioxolane, dimethoxyethane, dioxane, diethyl ether or dibutyl ether, water and DMF.
  • The above solvents can be used individually or in combination.
  • It is generally preferred that the solvent be used in an amount of 1 to 20 parts by weight, especially 3 to 8 parts by weight, and still especially 4 to 6 parts by weight, per 100 parts by weight of alkali metal hydride.
    • Reaction condition (reduction step A)
  • In the reaction of crosslink-cyclized cyclopentenone and alkali metal hydride, it is generally preferred that the reaction temperature be in the range of about -10 to 100°C, especially -10 to 80°C, and still especially 0 to 30°C. It is generally preferred that the reaction time be in the range of 30 min to 24 hr, especially 2 to 8 hr. This reaction is preferably performed in an atmosphere of inert gas such as nitrogen gas.
  • The reduction reaction can be selectively advanced by carrying out the reaction of crosslink-cyclized cyclopentenone and alkali metal hydride under the above conditions to thereby enable obtaining the desired crosslink-cyclized cyclopentenol with high yield.
  • After the completion of the reaction, the product can be obtained by, for example, sequentially performing acid neutralization of a solution containing the reaction product, isolation and purification. Instead, without isolating the reaction product, the solution containing the reaction product can directly be subjected to the subsequent dehydration reaction (B) of formed crosslink-cyclized cyclopentenol. The product yield is generally in the range of about 70 to 90% based on the cyclopentenol.
  • The thus obtained product is crosslink-cyclized cyclopentenol of the general formula (II):
    Figure 00180001
       wherein R1, R2 and n are as defined above with respect to the general formula (I).
    • [Dehydration step B] Dehydrating agent
  • The dehydrating agent for use in the dehydration reaction of cyclopentenol of the general formula (II) in the dehydration step B of the present invention is preferably an acid dehydrating agent, still preferably a strong acid. As the acid dehydrating agent, there can be mentioned, for example, hydrochloric acid, paratoluenesulfonic acid and sulfuric acid.
  • It is preferred that the dehydrating agent be used in a molar amount of 0.01 to 1.0 time, especially 0.05 to 0.5 time, and still especially 0.10 to 0.25 time, that of the above crosslink-cyclized cyclopentenol.
    • Solvent (dehydration step B)
  • The dehydration reaction of the dehydration step B of the present invention is preferably performed in the presence of a solvent. Any solvents can be employed as long as they are inert to the reaction. For example, solvents used in the above reduction step A and hydrocarbon solvents can be employed as the solvent. In particular, in the dehydration step B, there can preferably be employed polar solvents capable of oil/water separation, for example, ether solvents such as tetrahydrofuran, 1,3-dioxolane, dimethoxyethane, dioxane, diethyl ether and dibutyl ether. These solvents can be used individually or in combination.
  • It is generally preferred that the solvent be used in an amount of 1 to 20 parts by weight, especially 3 to 10 parts by weight, and still especially 5 to 7 parts by weight, per 100 parts by weight of crosslink-cyclized cyclopentenol.
    • Reaction condition (dehydration step B)
  • In the reaction of crosslink-cyclized cyclopentenol and dehydrating agent, it is generally preferred that the reaction temperature be in the range of about -10 to 60°C, especially 0 to 40°C, and still especially 10 to 30°C. It is generally preferred that the reaction time be in the range of 1 to 48 hr, especially 4 to 12 hr. This reaction is preferably performed in an atmosphere of inert gas such as nitrogen gas.
  • The desired crosslink-cyclized cyclopentadiene can be obtained by carrying out the reaction of crosslink-cyclized cyclopentenol and dehydrating agent under the above conditions.
  • After the completion of the reaction, the product can be obtained by, for example, sequentially performing neutralization of a solution containing the reaction product, isolation and purification. The product yield is generally in the range of about 70 to 90% based on the cyclopentenone.
  • The thus obtained product is crosslink-cyclized cyclopentadiene of the general formula (III):
    Figure 00210001
       wherein R1, R2 and n are as defined above with respect to the general formula (I), and the broken line in the 5-membered ring denotes that the 5-membered ring has two double bonds.
  • The crosslink-cyclized cyclopentadiene obtained by the present invention can be, for example, any of: crosslink-cyclized cyclopentadienes of the general formula (III) wherein both R1 and R2 are hydrogen atoms, such as
       bicyclo[3,3,0]octadiene, bicyclo[4,3,0]nonadiene, bicyclo[5,3,0]decadiene, bicyclo[6,3,0]undecadiene, bicyclo[7,3,0]dodecadiene, bicyclo[8,3,0]tridecadiene, bicyclo[9,3,0]tetradecadiene, and bicyclo[10,3,0]pentadecadiene;
    crosslink-cyclized cyclopentadienes of the general formula (III) wherein either of R1 and R2 is an alkyl substituent, such as
       6-methylbicyclo[3,3,0]octadiene, 8-methylbicyclo[3,3,0]octadiene, 6-ethylbicyclo[3,3,0]octadiene, 8-ethylbicyclo[3,3,0]octadiene, 6-isopropylbicyclo[3,3,0]octadiene, 8-isopropylbicyclo[3,3,0]octadiene, 8-n-butylbicyclo[3,3,0]octadiene, 7-methylbicyclo[4,3,0]nonadiene, 9-methylbicyclo[4,3,0]nonadiene, 7-ethylbicyclo[4,3,0]nonadiene, 9-ethylbicyclo[4,3,0]nonadiene, 7-isopropylbicyclo[4,3,0]nonadiene, 9-isopropylbicyclo[4,3,0]nonadiene, 9-n-butylbicyclo[4,3,0]nonadiene, 8-methylbicyclo[5,3,0]decadiene, 10-methylbicyclo[5,3,0]decadiene, 8-ethylbicyclo[5,3,0]decadiene, 10-ethylbicyclo[5,3,0]decadiene, 8-isopropylbicyclo[5,3,0]decadiene, 10-isopropylbicyclo[5,3,0]decadiene, 10-n-butylbicyclo[5,3,0]decadiene, 9-methylbicyclo[6,3,0]undecadiene, 11-methylbicyclo[6,3,0]undecadiene, 9-ethylbicyclo[6,3,0]undecadiene, 11-ethylbicyclo[6,3,0]undecadiene, 9-isopropylbicyclo[6,3,0]undecadiene, 11-isopropylbicyclo[6,3,0]undecadiene, 11-n-butylbicyclo[6,3,0]undecadiene, 10-methylbicyclo[7,3,0]dodecadiene, 12-methylbicyclo[7,3,0]dodecadiene, 10-ethylbicyclo[7,3,0]dodecadiene, 12-ethylbicyclo[7,3,0]dodecadiene, 10-isopropylbicyclo[7,3,0]dodecadiene, 12-isopropylbicyclo[7,3,0]dodecadiene, 12-n-butylbicyclo[7,3,0]dodecadiene, 11-methylbicyclo[8,3,0]tridecadiene, 13-methylbicyclo[8,3,0]tridecadiene, 11-ethylbicyclo[8,3,0]tridecadiene, 13-ethylbicyclo[8,3,0]tridecadiene, 11-isopropylbicyclo[8,3,0]tridecadiene, 13-isopropylbicyclo[8,3,0]tridecadiene, 13-n-butylbicyclo[8,3,0]tridecadiene, 12-methylbicyclo[9,3,0]tetradecadiene, 14-methylbicyclo[9,3,0]tetradecadiene, 12-ethylbicyclo[9,3,0]tetradecadiene, 14-ethylbicyclo[9,3,0]tetradecadiene, 12-isopropylbicyclo[9,3,0]tetradecadiene, 14-isopropylbicyclo[9,3,0]tetradecadiene, 14-n-butylbicyclo[9,3,0]tetradecadiene, 13-methylbicyclo[10,3,0]pentadecadiene, 15-methylbicyclo[10,3,0]pentadecadiene, 13-ethylbicyclo[10,3,0]pentadecadiene, 15-ethylbicyclo[10,3,0]pentadecadiene, 13-isopropylbicyclo[10,3,0]pentadecadiene, 15-isopropylbicyclo[10,3,0]pentadecadiene, and 15-n-butylbicyclo[10,3,0]pentadecadiene; and
    crosslink-cyclized cyclopentadienes of the general formula (III) wherein both R1 and R2 are alkyl substituents, such as
       6,8-dimethylbicyclo[3,3,0]octadiene, 6,8-diethylbicyclo[3,3,0]octadiene, 6,8-diisopropylbicyclo[3,3,0]octadiene, 6-methyl-8-n-butylbicyclo[3,3,0]octadiene, 7,9-dimethylbicyclo[4,3,0]nonadiene, 7,9-diethylbicyclo[4,3,0]nonadiene, 7,9-diisopropylbicyclo[4,3,0]nonadiene, 7-methyl-9-n-butylbicyclo[4,3,0]nonadiene, 8,10-dimethylbicyclo[5,3,0]decadiene, 8,10-diethylbicyclo[5,3,0]decadiene, 8,10-diisopropylbicyclo[5,3,0]decadiene, 8-methyl-10-n-butylbicyclo[5,3,0]decadiene, 9,11-dimethylbicyclo[6,3,0]undecadiene, 9,11-diethylbicyclo[6,3,0]undecadiene, 9,11-diisopropylbicyclo[6,3,0]undecadiene, 9-methyl-11-n-butylbicyclo[6,3,0]undecadiene, 10,12-dimethylbicyclo[7,3,0]dodecadiene, 10,12-diethylbicyclo[7,3,0]dodecadiene, 10,12-diisopropylbicyclo[7,3,0]dodecadiene, 10-methyl-12-n-butylbicyclo[7,3,0]dodecadiene, 11,13-dimethylbicyclo[8,3,0]tridecadiene, 11,13-diethylbicyclo[8,3,0]tridecadiene, 11, 13-diisopropylbicyclo[8,3,0]tridecadiene, 11-methyl-13-n-butylbicyclo[8,3,0]tridecadiene, 12,14-dimethylbicyclo[9,3,0]tetradecadiene, 12,14-diethylbicyclo[9,3,0]tetradecadiene, 12,14-diisopropylbicyclo[9,3,0]tetradecadiene, 12-methyl-14-n-butylbicyclo[9,3,0]tetradecadiene, 13,15-dimethylbicyclo[10,3,0]pentadecadiene, 13,15-diethylbicyclo[10,3,0]pentadecadiene, 13,15-diisopropylbicyclo[10,3,0]pentadecadiene, and 13-methyl-15-n-butylbicyclo[10,3,0]pentadecadiene.
  • The double bonds of these diene compounds may contain position isomers as a result of isomerization.
    • [Crosslink-cyclized cyclopentadiene]
  • Among the crosslink-cyclized cyclopentadienes, the second invention provides crosslink-cyclized cyclopentadienes of the general formula (IV):
    Figure 00260001
       wherein each of R1 and R2 independently represents a linear or branched saturated alkyl group having 1 to 6 carbon atoms, n is an integer of 3 to 10, and the broken line in the 5-membered ring denotes that the 5-membered ring has two double bonds. These crosslink-cyclized cyclopentadienes are novel compounds, examples of which include
       6,8-dimethylbicyclo[3,3,0]octadiene, 6,8-diethylbicyclo[3,3,0]octadiene, 6,8-diisopropylbicyclo[3,3,0]octadiene, 6-methyl-8-n-butylbicyclo[3,3,0]octadiene, 7,9-dimethylbicyclo[4,3,0]nonadiene, 7,9-diethylbicyclo[4,3,0]nonadiene, 7,9-diisopropylbicyclo[4,3,0]nonadiene, 7-methyl-9-n-butylbicyclo[4,3,0]nonadiene, 8,10-dimethylbicyclo[5,3,0]decadiene, 8,10-diethylbicyclo[5,3,0]decadiene, 8,10-diisopropylbicyclo[5,3,0]decadiene, 8-methyl-10-n-butylbicyclo[5,3,0]decadiene, 9,11-dimethylbicyclo[6,3,0]undecadiene, 9,11-diethylbicyclo[6,3,0]undecadiene, 9,11-diisopropylbicyclo[6,3,0]undecadiene, 9-methyl-11-n-butylbicyclo[6,3,0]undecadiene, 10,12-dimethylbicyclo[7,3,0]dodecadiene, 10,12-diethylbicyclo[7,3,0]dodecadiene, 10,12-diisopropylbicyclo[7,3,0]dodecadiene, 10-methyl-12-n-butylbicyclo[7,3,0]dodecadiene, 11,13-dimethylbicyclo[8,3,0]tridecadiene, 11,13-diethylbicyclo[8,3,0]tridecadiene, 11,13-diisopropylbicyclo[8,3,0]tridecadiene, 11-methyl-13-n-butylbicyclo[8,3,0]tridecadiene, 12,14-dimethylbicyclo[9,3,0]tetradecadiene, 12,14-diethylbicyclo[9,3,0]tetradecadiene, 12,14-diisopropylbicyclo[9,3,0]tetradecadiene, 12-methyl-14-n-butylbicyclo[9,3,0]tetradecadiene, 13,15-dimethylbicyclo[10,3,0]pentadecadiene, 13,15-diethylbicyclo[10,3,0]pentadecadiene, 13,15-diisopropylbicyclo[10,3,0]pentadecadiene, and 13-methyl-15-n-butylbicyclo[10,3,0]pentadecadiene.
  • The double bonds of these diene compounds may contain position isomers as a result of isomerization.
    • [Dihalobis (η-crosslink-cyclized cyclopentadienyl)metal compound and process for producing thereof]
  • The dihalobis(η-crosslink-cyclized cyclopentadienyl)metal compound according to the third invention and the process for producing the same will now be described.
  • The dihalobis(η-crosslink-cyclized cyclopentadienyl)metal compound according to the present invention can be synthesized by reacting the above obtained crosslink-cyclized cyclopentadiene of the general formula (IV) with a metal halide in the presence of a base.
  • Specifically, the dihalobis (η-crosslink-cyclized cyclopentadienyl)metal compound can be synthesized by:
  • reacting a cyclopentenone of the general formula (I-1) with an alkali metal hydride;
    Figure 00290001
       wherein each of R1 and R2 independently represents a hydrogen atom or a linear or branched saturated alkyl group having 1 to 6 carbon atoms, and n is an integer of 3 to 10,
  • to thereby reduce the cyclopentenone (reduction step A) into a cyclopentenol of the general formula (II-1):
    Figure 00290002
       wherein R1, R2 and n are as defined above with respect to the general formula (I-1);
  • reacting the cyclopentenol with a dehydrating agent to thereby dehydrate the cyclopentenol (dehydration step
  • B) into a crosslink-cyclized cyclopentadiene of the general formula (IV):
    Figure 00300001
       wherein R1, R2 and n are as defined above with respect to the general formula (I-1), and the broken line in the 5-membered ring denotes that the 5-membered ring has two double bonds; and
  • reacting the obtained crosslink-cyclized cyclopentadiene with a metal halide in the presence of a base.
  • In the reaction of the cyclopentadiene with a metal halide in the presence of a base for obtaining the dihalobis (η-crosslink-cyclized cyclopentadienyl)metal compound, use can be made of an inert solvent. For example, the process comprising reacting the crosslink-cyclized cyclopentadiene with a base in a solvent in advance and mixing the resultant reaction mixture with a metal halide suspension is preferably employed.
  • The base for use in the present invention can be, for example, n-butyllithium or sodium hydride.
  • As the solvent for use to mix the crosslink-cyclized cyclopentadiene and the base in advance, there can be employed solvents inert to the reaction, for example, an ether such as tetrahydrofuran, 1,3-dioxolane, dimethoxyethane, dioxane, diethyl ether or dibutyl ether, a saturated aliphatic or alicyclic solvent such as n-hexane or cyclohexane and an aromatic solvent such as toluene or benzene.
  • It is generally preferred that the base be used in a molar amount of 0.8 to 1.5 times, especially 0.9 to 1.2 times, and still especially 0.98 to 1.08 times, that of the above crosslink-cyclized cyclopentadiene.
  • The temperature at which the crosslink-cyclized cyclopentadiene is reacted with the base is generally in the range of -20 to 50°C, preferably 0 to 30°C. The reaction time is generally in the range of 30 to 48 hr, preferably 5 to 30 hr.
  • The metal halide compound for use in the present invention can be any of a titanium halide, a zirconium halide and a hafnium halide. Of these, a zirconium halide is preferably employed. For example, the metal halide compound can be any of fluorides, chlorides, bromides and iodides of titaniums (II), (III) and (IV); fluorides, chlorides, bromides and iodides of zirconiums (II), (III) and (IV); and fluorides, chlorides, bromides and iodides of hafniums (II), (III) and (IV). Of these, titanium (IV), zirconium (IV) and hafnium (IV) halides are preferred, and titanium tetrachloride, zirconium tetrachloride and hafnium tetrachloride are especially preferred.
  • As the solvent for suspending the metal halide compound, there can be employed solvents inert to the reaction, for example, hexane, heptane, toluene and ethers such as tetrahydrofuran, 1,3-dioxolane, dimethoxyethane, dioxane, diethyl ether and dibutyl ether.
  • It is preferred that the metal halide be used in a molar amount of 0.3 to 0.8 time, especially 0.4 to 0.6 time, and still especially 0.45 to 0.55 time, that of the crosslink-cyclized cyclopentadiene.
  • The dihalobis(η-crosslink-cyclized cyclopentadienyl)metal compound of the present invention can be obtained by adding the suspension of metal halide to the reaction mixture of crosslink-cyclized cyclopentadiene and base to thereby effect a reaction therebetween. The reaction temperature is generally in the range of -20 to 50°C, preferably 0 to 30°C. The reaction time is generally in the range of 3 to 72 hr, preferably 10 to 48 hr.
  • The thus obtained dihalobis(η-crosslink-cyclized cyclopentadienyl)metal compound is represented by the following general formula (V), and finds applications as an olefin polymerization catalyst, as a carbometallization agent for acetylene compounds, in the synthesis of a starting material of monohydride homologues and as a vulcanizing agent for silicones and rubbers;
    Figure 00330001
       wherein each of R1 and R2 independently represents a linear or branched saturated alkyl group having 1 to 6 carbon atoms; n is an integer of 3 to 10; M represents Ti, Zr or Hf; and X represents a halogen atom selected from among a chlorine atom, a bromine atom, an iodine atom and a fluorine atom.
  • The dihalobis (η-crosslink-cyclized cyclopentadienyl)metal compounds of the general formula (V) are novel compounds. As examples thereof, there can be mentioned dihalobis (η-crosslink-cyclized cyclopentadienyl)metal compounds formed by reactions between crosslink-cyclized cyclopentadienes as set forth above as particular compounds of the general formula (IV) and titanium, zirconium and hafnium halides. Preferred products are, for example, dichlorobis (η-crosslink-cyclized cyclopentadienyl) titanium, dichlorobis (η-crosslink-cyclized cyclopentadienyl)zirconium and dichlorobis (η-crosslink-cyclized cyclopentadienyl)hafnium.
    • EFFECT OF THE INVENTION
  • The process for producing a crosslink-cyclized cyclopentadiene according to the first invention enables producing a crosslink-cyclized cyclopentadiene with high yield under mild conditions without the need to install special apparatus. Further, the second invention enables providing a novel crosslink-cyclized cyclopentadiene. Still further, the third invention enables providing a dihalobis (η-crosslink-cyclized cyclopentadienyl)metal compound containing the above crosslink-cyclized cyclopentadiene as ligands.
    • EXAMPLE Example 1 [Synthesis of 7,9-dimethylbicyclo[4,3,0]nona-1(9)-en-8-ol]
  • Methanol (4 g) solution containing 1.64 g (10 mmol) of 7,9-dimethylbicyclo[4,3,0]nona-1(9)-en-8-one prepared by the method of J. Am. Chem. Soc., 100, 1799 (1978) was dropped over a period of 10 min into a suspension obtained by suspending 0.76 g (20 mmol) of sodium borohydride in 5 g of tetrahydrofuran (THF). The mixture was agitated at room temperature (25°C) for 4 hr. The thus obtained reaction mixture was cooled to 10°C or below, and-10 g of 2 N hydrochloric acid was dropped thereinto so as to effect neutralization with the pH value adjusted to 7. 10 g of ethyl acetate was added to the reaction mixture. An organic layer was separated, washed with water and dried over sodium sulfate. The sodium sulfate was filtered off, and the solvent was distilled off in vacuum. Thus, 1.94 g of colorless oily compound was obtained (73% purity and 85% yield).
  • The thus obtained compound was incorporated in CDCl3 and analyzed by 1H-NMR (400 MHz). It was found that the compound was 7,9-dimethylbicyclo[4,3,0]non-1(9)-en-8-ol. Spectrum chart obtained by the 1H-NMR (400 MHz) analysis is shown in Fig. 1.
    • [Synthesis of 7,9-dimethylbicyclo[4,3,0]nonadiene]
  • 2 g of 2 N hydrochloric acid was dropped into a solution obtained by dissolving 3.38 g (15 mmol) of the above obtained 7,9-dimethylbicyclo[4,3,0]non-1(9)-en-8-ol in 10 g of cyclohexane and 10 g of THF, and agitated at room temperature (25°C) for 9 hr. A saturated aqueous solution of NaHCO3 (4 mmol) was added to the reaction mixture so as to adjust the pH value to 9. 10 g of cyclohexane was added to the resultant reaction mixture. An organic layer was separated, washed with water and dried over sodium sulfate. The sodium sulfate was filtered off, and the solvent was distilled off in vacuum. Thus, 3.15 g of colorless oily compound was obtained. The purity was 63%, and the yield was 90% based on the 7,9-dimethylbicyclo[4,3,0]nona-1(9)-en-8-ol.
  • The thus obtained compound was incorporated in CDCl3 and analyzed by 1H-NMR (400 MHz). It was found that the compound was 7,9-dimethylbicyclo[4,3,0]nonadiene. Spectrum chart obtained by the 1H-NMR (400 MHz) analysis is shown in Fig. 2.
    • Example 2 [Synthesis of dichlorobis{7,9-dimethylbicyclo[4,3,0]nonadienyl}zirconium]
  • A THF (6g) solution containing 2.35 g (10 mmol) of 7,9-dimethylbicyclo[4,3,0]nonadiene synthesized in the same manner as in Example 1 was cooled to 5°C in a nitrogen atmosphere. 6.5 ml (1.6 mmol) of a hexane solution of n-BuLi (10.4 mmol) was dropped into the solution. After the dropping, the reaction mixture was slowly heated up to room temperature (25°C). At this temperature, the mixture was agitated for 24 hr. Thus, a yellowish-brown suspension was obtained. The obtained yellowish-brown suspension was dropped into a suspension of 1.16 g (5 mmol) of zirconium tetrachloride in 10 g of heptane while maintaining the temperature at 10°C or below by cooling with ice. Thereafter, the reaction mixture was heated up to room temperature (25°C) and agitated for 48 hr. Thus, a blackish-brown suspension was obtained. This blackish-brown suspension was filtered to thereby obtain a yellowish-brown solution, from which the solvent was distilled off. Thus, 1.02 g of yellowish-brown viscous oil was obtained. 10 g of heptane was added to the yellowish-brown viscous oil. Precipitated crystal was collected by filtration. Thus, 20 mg of desired crystal was obtained. The purity was about 90%, and the yield was 1% based on the 7,9-dimethylbicyclo[4,3,0]nonadiene.
  • The thus obtained compound was incorporated in CDCl3 and analyzed by 1H-NMR (400 MHz). It was found that the compound was dichlorobis{7,9-dimethylbicyclo[4,3,0]nonadienyl}zirconium. Spectrum chart obtained by the 1H-NMR (400 MHz) analysis is shown in Fig. 3.

Claims (9)

  1. A process for producing a crosslink-cyclized cyclopentadiene, comprising the steps of:
    reacting a cyclopentenone of the general formula (I) with an alkali metal hydride;
    Figure 00390001
       wherein each of R1 and R2 independently represents a hydrogen atom or a linear or branched saturated alkyl group having 1 to 6 carbon atoms, and n is an integer of 3 to 10,
    to thereby reduce the cyclopentenone (reduction step A) into a cyclopentenol of the general formula (II):
    Figure 00390002
       wherein R1, R2 and n are as defined above; and
    reacting the cyclopentenol with a dehydrating agent to thereby dehydrate the cyclopentenol (dehydration step B) into a crosslink-cyclized cyclopentadiene of the general formula (III):
    Figure 00400001
       wherein R1, R2 and n are as defined above, and the broken line in the 5-membered ring denotes that the 5-membered ring has two double bonds.
  2. The process as claimed in claim 1, wherein the alkali metal hydride is an alkali metal borohydride compound.
  3. The process as claimed in claim 1, wherein the alkali metal hydride is sodium borohydride or potassium borohydride.
  4. The process as claimed in any of claims 1 to 3, wherein the reduction step A is performed at -10 to 100°C.
  5. The process as claimed in any of claims 1 to 4, wherein the dehydrating agent is a strong acid.
  6. The process as claimed in any of claims 1 to 5, wherein the dehydration step B is performed at -10 to 100°C.
  7. A crosslink-cyclized cyclopentadiene of the general formula (IV):
    Figure 00410001
       wherein each of R1 and R2 independently represents a linear or branched saturated alkyl group having 1 to 6 carbon atoms, n is an integer of 3 to 10, and the broken line in the 5-membered ring denotes that the 5-membered ring has two double bonds.
  8. A dihalobis (η-crosslink-cyclized cyclopentadienyl)metal compound of the general formula (V):
    Figure 00420001
       wherein each of R1 and R2 independently represents a linear or branched saturated alkyl group having 1 to 6 carbon atoms; n is an integer of 3 to 10; M represents Ti, Zr or Hf; and X represents a halogen atom selected from among a chlorine atom, a bromine atom, an iodine atom and a fluorine atom.
  9. A process for producing a dihalobis (η-crosslink-cyclized cyclopentadienyl)metal compound claimed in claim 8, comprising reacting a cyclopentadiene of the general formula (IV) with a metal halide;
    Figure 00430001
       wherein each of R1 and R2 independently represents a linear or branched saturated alkyl group having 1 to 6 carbon atoms, n is an integer of 3 to 10, and the broken line in the 5-membered ring denotes that the 5-membered ring has two double bonds,
       said reaction being performed in the presence of a base.
EP01300942A 2000-02-03 2001-02-02 Process for the preparation of condensed cyclopentadiene derivatives, 1, 3 disubstituted derivatives and metallocene type compounds containing them as ligand Expired - Lifetime EP1122229B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000026835A JP4246871B2 (en) 2000-02-03 2000-02-03 Bridged cyclic cyclopentadiene and dihalobismetal compound having it as a ligand
JP2000026835 2000-02-03

Publications (2)

Publication Number Publication Date
EP1122229A1 true EP1122229A1 (en) 2001-08-08
EP1122229B1 EP1122229B1 (en) 2006-04-26

Family

ID=18552509

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01300942A Expired - Lifetime EP1122229B1 (en) 2000-02-03 2001-02-02 Process for the preparation of condensed cyclopentadiene derivatives, 1, 3 disubstituted derivatives and metallocene type compounds containing them as ligand

Country Status (4)

Country Link
US (1) US6482966B2 (en)
EP (1) EP1122229B1 (en)
JP (1) JP4246871B2 (en)
DE (1) DE60118994T2 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2768307B1 (en) * 2011-10-19 2020-03-18 Bikam Pharmaceuticals, Inc. Opsin-binding ligands, compositions and methods of use
EP2679594A1 (en) * 2012-06-25 2014-01-01 Daelim Industrial Co., Ltd. Metallocene compound, catalyst composition including the same, and olefin polymerization process using the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0283739A2 (en) * 1987-03-10 1988-09-28 Chisso Corporation Bis (di-, tri- or tetra-substituted-cyclopentadienyl)-zirconium dihalides
EP0760355A1 (en) * 1995-08-30 1997-03-05 ENICHEM S.p.A. Cyclopentadienyl derivatives and process for their preparation
JPH10182714A (en) * 1996-12-24 1998-07-07 Idemitsu Petrochem Co Ltd Transition metal compound, catalyst for polymerization using the same and polymerization
JPH10316694A (en) * 1997-03-18 1998-12-02 Idemitsu Petrochem Co Ltd Transition metal compound, polymerization catalyst using the same and production of polymer in presence of the polymerization catalyst

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1276084B1 (en) * 1995-11-07 1997-10-24 Enichem Spa CYCLOPENTADIENIL BRIDGED DERIVATIVES AND PROCEDURE FOR THEIR PREPARATION

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0283739A2 (en) * 1987-03-10 1988-09-28 Chisso Corporation Bis (di-, tri- or tetra-substituted-cyclopentadienyl)-zirconium dihalides
EP0760355A1 (en) * 1995-08-30 1997-03-05 ENICHEM S.p.A. Cyclopentadienyl derivatives and process for their preparation
JPH10182714A (en) * 1996-12-24 1998-07-07 Idemitsu Petrochem Co Ltd Transition metal compound, catalyst for polymerization using the same and polymerization
JPH10316694A (en) * 1997-03-18 1998-12-02 Idemitsu Petrochem Co Ltd Transition metal compound, polymerization catalyst using the same and production of polymer in presence of the polymerization catalyst

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
AUSTIN, RACHEL N. ET AL: "Synthesis and properties of novel substituted 4,5,6,7- tetrahydroindenes and selected metal complexes", J. ORGANOMET. CHEM. (1995), 491(1-2), 11-18, 1995, XP004024121 *
English Translation of the claims *

Also Published As

Publication number Publication date
JP4246871B2 (en) 2009-04-02
JP2001213809A (en) 2001-08-07
DE60118994D1 (en) 2006-06-01
US20010012902A1 (en) 2001-08-09
DE60118994T2 (en) 2006-09-07
EP1122229B1 (en) 2006-04-26
US6482966B2 (en) 2002-11-19

Similar Documents

Publication Publication Date Title
JPH06122692A (en) Method of preparing bisindenyl bridged chiral metallocene catalyst
JPH05148166A (en) New fluorenyl compound and preparation thereof
US6043403A (en) Process for the preparation of cyclopentadienyl compounds and compounds obtained therefrom
EP1963339B1 (en) Process for recycling cyclopentdienyl derivatives and preapring metallocenes from recycle, substituted cyclopentdienyl derivatives
EP0920403B1 (en) Process for preparing cyclopentadienyl compounds
EP0295880B1 (en) Substituted cyclic ketones, substituted cyclic enones, and process for producing the same
Halterman et al. Application of the double Pauson-Khand cyclization to the synthesis of bis (cyclopentadienes): preparation of phenyl-bridged bis (tetrahydroindenyl) titanium and zirconium dichlorides
US5912373A (en) Process for converting the achiral meso form of an ansa-metallocene complex into the chiral racemic form
US6482966B2 (en) Crosslink-cyclized cyclopentadiene and dihalobis type metal compound containing same as ligand
WO2023096802A1 (en) Monoalkyl cyclopentadiene compounds and processes for preparing same
JPH069483A (en) Production of substituted indanones
US11566037B2 (en) Process for producing isopropylidene bis(cyclopentadienyl)zirconium dichloride
WO2000040528A1 (en) Pentafulvene synthesis
JP2917552B2 (en) Method for producing α-methylenecyclopentanone derivative
EP0920432B1 (en) Preparation and separation of rac and meso compound mixtures
RU2374255C2 (en) Method of producing 2,3-dialkyl-5-alkylidenemagnesa-cyclopent-2-enes
RU2397174C2 (en) 2,3,4,5-tetraalkylmagnesacyclopenta-2,4-diene synthesis method
KR20240073969A (en) Method for producing organo-titanium compounds
US5231208A (en) Substituted cyclic ketones, substituted cyclic enones, and process for producing the same
US6414206B2 (en) Process for preparing bisindenylalkanes
WO1997019906A1 (en) Tricyclocarboxylate, method for preparing the same and perfume comprising the same
RU2130024C1 (en) Method of combined preparation of 1-(alkoxy)-2,3,4,5- tetraalkyl-(aryl) alumacyclopentadienes and 1-(alkoxy)- 2,3-dialkyl (aryl)alumacyclopropenes
JPS5936898B2 (en) Production method of methyl diasmonate
JPH0557247B2 (en)
JPS6117531A (en) 6-substituted tetrahydroindanone and its preparation

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT NL

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20020123

AKX Designation fees paid

Free format text: DE FR GB IT NL

17Q First examination report despatched

Effective date: 20020903

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20060426

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60118994

Country of ref document: DE

Date of ref document: 20060601

Kind code of ref document: P

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20070129

EN Fr: translation not filed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20070202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070309

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070202

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20080225

Year of fee payment: 8

Ref country code: NL

Payment date: 20080229

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060426

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20090901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090901